Passivated Cement Accelerator

ABSTRACT

Embodiments relate to cementing operations and, in certain embodiments, to passivated cement accelerators and methods of using passivated cement accelerators in subterranean formations. An embodiment may comprise a method of cementing comprising: providing a cement composition comprising cement, water, and a passivated cement accelerator; and allowing the cement composition to set.

BACKGROUND

Embodiments relate to cementing operations and, in certain embodiments,to passivated cement accelerators and methods of using passivated cementaccelerators in subterranean formations.

Cement compositions may be used in a variety of subterranean operations.For example, in subterranean well construction, a pipe string (e.g.,casing, liners, expandable tubulars, etc.) may be run into a wellboreand cemented in place. The process of cementing the pipe string in placeis commonly referred to as “primary cementing.” In a typical primarycementing method, a cement composition may be pumped into an annulusbetween the walls of the wellbore and the exterior surface of the pipestring disposed therein. The cement composition may set in the annularspace, thereby forming an annular sheath of hardened, substantiallyimpermeable cement (i.e., a cement sheath) that may support and positionthe pipe string in the wellbore and may bond the exterior surface of thepipe string to the subterranean formation. Among other things, thecement sheath surrounding the pipe string functions to prevent themigration of fluids in the annulus, as well as protecting the pipestring from corrosion. Cement compositions also may be used in remedialcementing methods, for example, to seal cracks or holes in pipe stringsor cement sheaths, to seal highly permeable formation zones orfractures, to place a cement plug, and the like.

A broad variety of cement compositions have been used in subterraneancementing operations. In some instances, a cement accelerator may beused to accelerate strength development of the cement. For example, acement accelerator may be added to a cement composition to provideappreciable strength to the cement composition in the early stages ofstrength development (e.g., within 24 hours at temperatures below 160°F.). Among other reasons, a cement accelerator may be suitable for usein wellbore applications, for example, where it is desired to reduce thelength of an operation (e.g., by reducing the period of hydration).Cement accelerators may also be suitable to counter the retardingeffects of low temperature, such as in operations near the surface, orin systems where additives that may retard the cement have been used.

While cement accelerators have been developed heretofore, challengesexist with their successful use in subterranean cementing operations.For example, cement accelerators may have undesired gelation issueswhich can limit their use and effectiveness in cementing operations.These issues may persist even with the presence of dispersants. Further,some cement accelerators may induce flash setting. Flash setting canmake the cement difficult to place, can damage the formation, and maylead to operational delays and an increase in operational costs.Traditional cement accelerators that have been developed, for example,those comprising CaCl₂, may be effective in some operations but may havelimited use in some types of cements or in cements that have beenretarded with some types of additives. For example, CaCl₂ is typicallynot useable at temperatures as low as 40° F., furthermore CaCl₂ has beenknown to corrode wellbore equipment and thus increase costs as well asthe risk of formation damage.

BRIEF DESCRIPTION OF THE DRAWINGS

These drawings illustrate certain aspects of some of the embodiments ofthe present method, and should not be used to limit or define themethod.

FIG. 1 illustrates a system for preparation and delivery of a cementcomposition to a wellbore in accordance with certain embodiments.

FIG. 2 illustrates surface equipment that may be used in placement of acement composition in a wellbore in accordance with certain embodiments.

FIG. 3 illustrates placement of a cement composition into a wellboreannulus in accordance with certain embodiments.

DESCRIPTION OF PREFERRED EMBODIMENTS

Embodiments relate to cementing operations and, in certain embodiments,to passivated cement accelerators and methods of using passivated cementaccelerators in subterranean formations. Cement compositions comprisingpassivated cement accelerators may be used in a variety of cementingoperations including surface cementing operations (e.g., construction)and subterranean cementing operations (e.g., primary and remedialcementing). One of the many potential advantages to these methods andcompositions is that they may increase early strength development, butnot induce or contribute to gelation or flash setting. Additionally, themethods and compositions herein provide a low cost, logistical means ofaccelerating early strength development as well as adding compressivestrength to a cement composition, whereas typical accelerators merelyaccelerate the strength development of the cement.

An example cement composition may comprise cement and water. Optionally,the cement composition may further comprise lime, dispersant, and/or aset retarder. As discussed in more detail below, a passivated cementaccelerator may be used, for example, to increase the early strengthdevelopment of the cement composition. The cement compositions may besuitable for a number of subterranean cementing operations, includingsubterranean formations having relatively low temperatures, e.g.,temperatures ranging from about 40° F. or lower to about 200° F.; and insubterranean formations having temperatures up to about 500° F. orhigher. In particular embodiments, the cement compositions may be usedin subterranean formations having a temperature range of about 40° F. toabout 240° F.

The cement composition may comprise cement. Any of a variety of cementsmay be suitable including those comprising calcium, aluminum, silicon,oxygen, iron, and/or sulfur, which set and harden by reaction withwater. Specific examples of cements that may be suitable include, butare not limited to, Portland cements, pozzolana cements, gypsum cements,high alumina content cements, silica cements, slag cements, and anycombination thereof. Examples of suitable Portland cements may includethose classified as Classes A, B, C, G, or H cements according toAmerican Petroleum Institute, API Specification for Materials andTesting for Well Cements, API Specification 10, Fifth Ed., Jul. 1, 1990.Additional examples of suitable Portland cements may include thoseclassified as ASTM Type I, II, III, IV, or V.

Embodiments of the cement may comprise pumice, a pozzelana cementitiousmaterial. Generally, pumice is a volcanic rock that can exhibitcementitious properties in that it may set and harden in the presence ofhydrated lime and water. The pumice may also be ground. Generally, thepumice may have any particle size distribution as desired for aparticular application. In certain embodiments, the pumice may have ad50 particle size distribution in a range of from about 1 micron toabout 200 microns. The d50 values may be measured by particle sizeanalyzers such as those manufactured by Malvern Instruments,Worcestershire, United Kingdom. In specific embodiments, the pumice mayhave a d50 particle size distribution in a range of from about 1 micronto about 200 microns, from about 5 microns to about 100 microns, or fromabout 10 microns to about 25 microns. In one particular embodiment, thepumice may have a d50 particle size distribution of about 15 microns orless. An example of a suitable pumice is DS-325 lightweight aggregateavailable from Hess Pumice Products, Inc., Malad, Id., and has a d50particle size distribution of about 15 microns or less. It should beappreciated that particle sizes too small may have mixability problemswhile particle sizes too large may not be effectively suspended in thecompositions. One of ordinary skill in the art, with the benefit of thisdisclosure, should be able to select a particle size for the pumicesuitable for a chosen application.

Embodiments of the cement may comprise slag. Slag is generally agranulated, blast furnace by-product from the production of cast ironcomprising the oxidized impurities found in iron ore. The slag may beincluded in embodiments of the hydraulic cement in an amount suitablefor a particular application.

Embodiments of the cement may comprise fly ash, a pozzolana cementitiousmaterial. A variety of fly ash may be suitable, including fly ashclassified as Class C and Class F fly ash according to AmericanPetroleum Institute, API Specification for Materials and Testing forWell Cements, API Specification 10, Fifth Ed., Jul. 1, 1990. Class C flyash comprises both silica and lime, so it may set to form a hardenedmass upon mixing with water. Class F fly ash generally does not containa sufficient amount of lime to induce a cementitious reaction,therefore, an additional source of calcium ions is necessary for acement composition comprising Class F fly ash. In some embodiments, limemay be mixed with Class F fly ash in an amount in the range of about0.1% to about 100% by weight of the fly ash. In some instances, the limemay be hydrated lime. Suitable examples of fly ash include, but are notlimited to, POZMIX® A cement additive, available from Halliburton EnergyServices, Inc., Houston, Tex.

Embodiments of the cement may comprise a high alumina content cement. Insome embodiments, a high alumina cement comprises a calcium aluminate.The calcium aluminate may be any calcium aluminate suitable for use as acement. A suitable calcium aluminate is SECAR® 60 calcium aluminate,available from Lonestar Lafarge Company. The high alumina content cementmay further comprise a soluble phosphate. Among other things, it isbelieved that the soluble phosphate should react with the high aluminacontent cement to form a set cement that may be resistant to carbondioxide. For example, calcium aluminate should react with sodiumpolyphosphate to form a calcium phosphate cement. Any type of solublephosphate may be included in the high alumina content cement, examplesinclude but are not limited to, vitreous sodium phosphates, sodiumhexametaphosphates, sodium polyphosphates, sodium dihydrogen phosphates,sodium monohydrogen phosphates, and combinations thereof. Other solublealkali phosphates also may be suitable for use. A suitable solublephosphate is available from Astaris LLC, St. Louis, Mo.

The cement may be included in the cement compositions in an amountsuitable for a particular application. The concentration of the cementmay also be selected, for example, to provide a particular compressivestrength for the cement composition after setting. Where used, thecement may be included in an amount in a range of from about 1% to about99% by weight of the cement. By way of example, the cement may bepresent in an amount ranging between any of and/or including any ofabout 1%, about 5%, about 10%, about 20%, about 30%, about 40%, about50, about 60%, about 70%, about 80%, about 90%, or about 99% by weightof the cement. In one particular embodiment, the cement may be presentin an amount in a range of from about 25% to about 75% by weight of thecement and, alternatively, from about 40% to 60% by weight of thecement. In some embodiments, the cementitious components present in thecement composition may consist essentially of the cement. For example,the cement composition may primarily comprise cement and water withoutany additional components that hydraulically set in the presence ofwater. One of ordinary skill in the art, with the benefit of thisdisclosure, should recognize the appropriate amount of cement to includefor a chosen application.

The water used in embodiments of the cement compositions may be from anysource provided that it does not contain an excess of compounds that mayundesirably affect other components in the cement compositions. Forexample, a cement composition may comprise fresh water or salt water.Salt water generally may include one or more dissolved salts therein andmay be saturated or unsaturated as desired for a particular application.Seawater or brines may be suitable for use in embodiments. Further, thewater may be present in an amount sufficient to form a pumpable slurry.In certain embodiments, the water may be present in the cementcomposition in an amount in the range of from about 33% to about 200% byweight of the cement. In certain embodiments, the water may be presentin the cement compositions in an amount in the range of from about 35%to about 70% by weight of the cement. One of ordinary skill in the artwith the benefit of this disclosure will recognize the appropriateamount of water for a chosen application.

Embodiments of the cement compositions may comprise a calcium ionsource. Suitable calcium ion sources may comprise any compound such as acalcium-containing salt or other species that is capable of dissociationto give calcium ions. In some embodiments, the calcium ion source may becapable of reacting with any other constituent of the cement compositionas to form a cementitious material. For example, suitable calcium ionsources may be capable of reacting with pumice in the presence of waterso as to form a cementitious material. Examples of calcium ion sourcesinclude: hydrated lime (which may alternatively be referred to as e.g.,calcium hydroxide, slaked lime, builder's lime, and/or slack lime);quick lime (which may alternatively be referred to as e.g., calciumoxide); and calcium salts in the presence of a hydroxide ion source.Calcium salts according to some embodiments may be of the form CaX₂,where X is an anion with a formal charge of −1 (e.g., CaBr₂, CaF₂, CaI₂,CaCl₂). Calcium salts according to other embodiments may be of the formCaX, where X is an anion with a formal charge of −2 (e.g., carbonateanion CO₃ ⁻²). In some embodiments, a calcium ion source may beaccompanied by or otherwise combined with a hydroxide ion source in thecement composition. Such a source may include a hydroxide salt of analkali or alkaline earth element. Suitable hydroxide salts includesodium hydroxide, potassium hydroxide, and calcium hydroxide. In certainembodiments, the calcium ion source may be included in a cementcomposition and subjected to alkaline conditions (for example, in orderto support a pozzolanic reaction between the calcium ion source and thepozzolan of some cement compositions). In some embodiments, the calciumion source itself may be alkaline or may, upon disassociation, createalkaline conditions (e.g., such as would occur upon the dissociation ofcalcium hydroxide).

Where present, the calcium ion source may be included in the cementcompositions in an amount in the range of from about 10% to about 100%by weight of the cement, for example. In some embodiments, the calciumion source may be present in an amount ranging between any of and/orincluding any of about 10%, about 20%, about 40%, about 60%, about 80%,or about 100% by weight of the cement. One of ordinary skill in the art,with the benefit of this disclosure, will recognize the appropriateamount of the calcium ion source to include for a chosen application.

Embodiments of the cement compositions may comprise a set retarder, forexample, to delay the setting and/or retard the cement. A broad varietyof set retarders may be suitable for use in the cement compositions. Forexample, the set retarder may comprise phosphonic acids, such as aminotris(methylene phosphonic acid), ethylenediamine tetra(methylenephosphonic acid), diethylenetriamine penta(methylene phosphonic acid),etc.; lignosulfonates, such as sodium lignosulfonate, calciumlignosulfonate, etc.; salts such as stannous sulfate, lead acetate,monobasic calcium phosphate, organic acids, such as citric acid,tartaric acid, etc.; cellulose derivatives such as hydroxyl ethylcellulose (HEC) and carboxymethyl hydroxyethyl cellulose (CMHEC);synthetic co- or ter-polymers comprising sulfonate and carboxylic acidgroups such as sulfonate-functionalized acrylamide-acrylic acidco-polymers; borate compounds such as alkali borates, sodium metaborate,sodium tetraborate, potassium pentaborate; derivatives thereof, ormixtures thereof. Examples of suitable set retarders include, amongothers, phosphonic acid derivatives. One example of a suitable setretarder is Micro Matrix® cement retarder, available from HalliburtonEnergy Services, Inc. Generally, the set retarder may be present in thecement compositions in an amount sufficient to delay the setting for adesired time. In some embodiments, the set retarder may be present inthe cement compositions in an amount in the range of from about 0.01% toabout 10% by weight of the cement. In specific embodiments, the setretarder may be present in an amount ranging between any of and/orincluding any of about 0.01%, about 0.1%, about 1%, about 2%, about 4%,about 6%, about 8%, or about 10% by weight of the cement. An exampleembodiment of a cement composition may comprise pumice, hydrated lime,water, and a set retarder. One of ordinary skill in the art, with thebenefit of this disclosure, will recognize the appropriate amount of theset retarder to include for a chosen application.

As previously mentioned embodiments of the cement compositions mayoptionally comprise a dispersant. Examples of suitable dispersantsinclude, without limitation, sulfonated-formaldehyde-based dispersants(e.g., sulfonated acetone formaldehyde condensate), examples of whichmay include Daxad® 19 dispersant available from Geo Specialty Chemicals,Ambler, Pa. Other suitable dispersants may be polycarboxylated etherdispersants such as Liquiment® 5581F and Liquiment® 514L dispersantsavailable from BASF Corporation Houston, Tex.; or Ethacryl™ G dispersantavailable from Coatex, Genay, France. An additional example of asuitable available dispersant is CFR™-3 dispersant, available fromHalliburton Energy Services, Inc, Houston, Tex. The Liquiment® 514Ldispersant may comprise 36% by weight of the polycarboxylated ether inwater. While a variety of dispersants may be used in accordance withembodiments, polycarboxylated ether dispersants may be particularlysuitable for use in some embodiments. Without being limited by theory,it is believed that polycarboxylated ether dispersants maysynergistically interact with other components of a set-delayed orretarded cement composition. For example, it is believed that thepolycarboxylated ether dispersants may react with certain set retarders(e.g., phosphonic acid derivatives) resulting in formation of a gel thatsuspends the cementitious materials in the composition for an extendedperiod of time.

In some embodiments, the dispersant may be included in the cementcompositions in an amount in the range of from about 0.01% to about 5%by weight of the cement. In specific embodiments, the dispersant may bepresent in an amount ranging between any of and/or including any ofabout 0.01%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about4%, or about 5% by weight of the cement. One of ordinary skill in theart, with the benefit of this disclosure, will recognize the appropriateamount of the dispersant to include for a chosen application.

In some embodiments, a viscosifier may be included in the cementcompositions. The viscosifier may be included to optimize fluid rheologyand to stabilize the suspension. Without limitation, examples ofviscosifiers include swellable clays such as bentonite or biopolymerssuch as cellulose derivatives (e.g., hydroxyethyl cellulose,carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose). Anexample of a commercially available viscosifier is SA-1015™ availablefrom Halliburton Energy Services, Inc., Houston, Tex. The viscosifiermay be included in the cement compositions in an amount in the range offrom about 0.01% to about 0.5% by weight of the cement. In specificembodiments, the viscosifier may be present in an amount ranging betweenany of and/or including any of about 0.01%, about 0.05%, about 0.1%,about 0.2%, about 0.3%, about 0.4%, or about 0.5% by weight of thecement. One of ordinary skill in the art, with the benefit of thisdisclosure, will recognize the appropriate amount of viscosifier toinclude for a chosen application.

Other additives suitable for use in the cementing operations may also beadded to the cement compositions as desired for a particularapplication. Examples of such additives include, but are not limited to,foaming additives, strength-retrogression additives, lightweightadditives, gas-generating additives, mechanical-property-enhancingadditives, lost-circulation materials, fluid-loss-control additives,defoaming additives, thixotropic additives, and any combination thereof.Specific examples of these, and other, additives include crystallinesilica, fumed silica, silicates, salts, fibers, hydratable clays,microspheres, diatomaceous earth, natural pozzolan, zeolite, fly ash,rice hull ash, swellable elastomers, resins, any combination thereof,and the like. A person having ordinary skill in the art, with thebenefit of this disclosure, will readily be able to determine the typeand amount of additive useful for a particular application and desiredresult.

Optionally, foaming additives may be included in the cement compositionsto, for example, facilitate foaming and/or stabilize the resultant foamformed therewith. In particular, the cement compositions may be foamedwith a foaming additive and a gas. The foaming additive may include asurfactant or combination of surfactants that reduce the surface tensionof the water. By way of example, the foaming agent may comprise ananionic, nonionic, amphoteric (including zwitterionic surfactants),cationic surfactant, or mixtures thereof. Examples of suitable foamingadditives include, but are not limited to: betaines; anionic surfactantssuch as hydrolyzed keratin; amine oxides such as alkyl or alkenedimethyl amine oxides; cocoamidopropyl dimethylamine oxide; methyl estersulfonates; alkyl or alkene amidobetaines such as cocoamidopropylbetaine; alpha-olefin sulfonates; quaternary surfactants such astrimethyltallowammonium chloride and trimethylcocoammonium chloride; C8to C22 alkylethoxylate sulfates; and combinations thereof. Specificexamples of suitable foaming additives include, but are not limited to:mixtures of an ammonium salt of an alkyl ether sulfate, acocoamidopropyl betaine surfactant, a cocoamidopropyl dimethylamineoxide surfactant, sodium chloride, and water, mixtures of an ammoniumsalt of an alkyl ether sulfate surfactant, a cocoamidopropylhydroxysultaine surfactant, a cocoamidopropyl dimethylamine oxidesurfactant, sodium chloride, and water, hydrolyzed keratin; mixtures ofan ethoxylated alcohol ether sulfate surfactant, an alkyl or alkeneamidopropyl betaine surfactant, and an alkyl or alkene dimethylamineoxide surfactant; aqueous solutions of an alpha-olefinic sulfonatesurfactant and a betaine surfactant; and combinations thereof. Anexample of a suitable foaming additive is ZONESEALANTI™ 2000 agent,available from Halliburton Energy Services, Inc.

Optionally, strength-retrogression additives may be included in thecement compositions to, for example, prevent the retrogression ofstrength after the cement composition has been allowed to developcompressive strength when the cement composition is exposed to hightemperatures. These additives may allow the cement compositions to formas intended, preventing cracks and premature failure of the cementitiouscomposition. Examples of suitable strength-retrogression additives mayinclude, but are not limited to, amorphous silica, coarse graincrystalline silica, fine grain crystalline silica, or a combinationthereof.

Optionally, lightweight additives may be included in the cementcompositions to, for example, decrease the density of the cementcompositions. Examples of suitable lightweight additives include, butare not limited to, bentonite, coal, diatomaceous earth, expandedperlite, fly ash, gilsonite, hollow microspheres, low-density elasticbeads, nitrogen, pozzolan-bentonite, sodium silicate, combinationsthereof, or other lightweight additives known in the art.

Optionally, gas-generating additives may be included in the cementcompositions to release gas at a predetermined time, which may bebeneficial to prevent gas migration from the formation through thecement composition before it hardens. The generated gas may combine withor inhibit the permeation of the cement composition by formation gas.Examples of suitable gas-generating additives include, but are notlimited to, metal particles (e.g., aluminum powder) that react with analkaline solution to generate a gas.

Optionally, mechanical-property-enhancing additives may be included inthe cement compositions to, for example, ensure adequate compressivestrength and long-term structural integrity. These properties can beaffected by the strains, stresses, temperature, pressure, and impacteffects from a subterranean environment. Examples ofmechanical-property-enhancing additives include, but are not limited to,carbon fibers, glass fibers, metal fibers, mineral fibers, silicafibers, polymeric elastomers, latexes, and combinations thereof.

Optionally, lost-circulation materials may be included in the cementcompositions to, for example, help prevent the loss of fluid circulationinto the subterranean formation. Examples of lost-circulation materialsinclude but are not limited to, cedar bark, shredded cane stalks,mineral fiber, mica flakes, cellophane, calcium carbonate, groundrubber, polymeric materials, pieces of plastic, ground marble, wood, nuthulls, formica, corncobs, cotton hulls, and combinations thereof.

Optionally, fluid-loss-control additives may be included in the cementcompositions to, for example, decrease the volume of fluid that is lostto the subterranean formation. Properties of the cement compositions maybe significantly influenced by their water content. The loss of fluidcan subject the cement compositions to degradation or complete failureof design properties. Examples of suitable fluid-loss-control additivesinclude, but not limited to, certain polymers, such as hydroxyethylcellulose, carboxymethylhydroxyethyl cellulose, copolymers of2-acrylamido-2-methylpropanesul tonic acid and acrylamide orN,N-dimethylacrylamide, and graft copolymers comprising a backbone oflignin or lignite and pendant groups comprising at least one memberselected from the group consisting of2-acrylamido-2-methylpropanesulfonic acid, acrylonitrile, andN,N-dimethylacrylamide.

Optionally, defoaming additives may be included in the cementcompositions to, for example, reduce tendency for the cement compositionto foam during mixing and pumping of the cement compositions. Examplesof suitable defoaming additives include, but are not limited to, polyolsilicone compounds. Suitable defoaming additives are available fromHalliburton Energy Services, Inc., under the product name D-AIR™defoamers.

Optionally, thixotropic additives may be included in the cementcompositions to, for example, provide a cement composition that can bepumpable as a thin or low viscosity fluid, but when allowed to remainquiescent attains a relatively high viscosity. Among other things,thixotropic additives may be used to help control free water, createrapid gelation as the slurry sets, combat lost circulation, prevent“fallback” in annular column, and minimize gas migration. Examples ofsuitable thixotropic additives include, but are not limited to, gypsum,water soluble carboxyalkyl, hydroxyalkyl, mixed carboxyalkylhydroxyalkyl either of cellulose, polyvalent metal salts, zirconiumoxychloride with hydroxyethyl cellulose, or a combination thereof.

The components of the cement compositions may be combined in any orderdesired to form a cement composition that can be placed on a surfaceand/or into a subterranean formation. In addition, the components of thecement compositions may be combined using any mixing device compatiblewith the composition, including a bulk mixer, for example. In oneparticular example, a cement composition may be prepared by combiningthe dry components (which may be the cement component, for example) withwater. Liquid additives (if any) may be combined with the water beforethe water is combined with the dry components. The dry components may bedry blended prior to their combination with the water. For example, adry blend may be prepared that comprises the magnesium metal ore wasteand the cement component. Other suitable techniques may be used forpreparation of the cement compositions as will be appreciated by thoseof ordinary skill in the art in accordance with example embodiments.

Those of ordinary skill in the art will appreciate that embodiments ofthe cement compositions generally should have a density suitable for aparticular application. By way of example, the cement compositions mayhave a density in the range of from about 4 pounds per gallon (“lb/gal”)to about 20 lb/gal. In certain embodiments, the cement compositions mayhave a density in the range of from about 8 lb/gal to about 17 lb/gal.Embodiments of the cement compositions may be foamed or unfoamed or maycomprise other means to reduce their densities, such as hollowmicrospheres, low-density elastic beads, or other density-reducingadditives known in the art. In embodiments, the density may be reducedafter storing the composition, but prior to placement in a subterraneanformation. Those of ordinary skill in the art, with the benefit of thisdisclosure, will recognize the appropriate density for a particularapplication.

Embodiments of the cement compositions may be set-delayed in that theyremain in a pumpable fluid state for one day or longer (e.g., about 1day, about 2 weeks, about 2 years or more) at room temperature (e.g.,about 80° F.) in quiescent storage. For example, the set-delayed cementcompositions may remain in a pumpable fluid state for a period of timefrom about 1 day to about 7 days or more. In some embodiments, theset-delayed cement compositions may remain in a pumpable fluid state forabout 1 day, about 7 days, about 10 days, about 20 days, about 30 days,about 40 days, about 50 days, about 60 days, or longer. A fluid isconsidered to be in a pumpable fluid state where the fluid has aconsistency of less than 70 Bearden units of consistency (“Bc”), asmeasured on a pressurized consistometer in accordance with the procedurefor determining cement thickening times set forth in API RP Practice10B-2, Recommended Practice for Testing Well Cements, First Edition.July 2005. An example embodiment of a cement composition that has beenset-delayed may comprise pumice, hydrated lime, water, a set retarder,and optionally a dispersant.

Embodiments may generally utilize a passivated cement accelerator toincrease early strength development. As used herein, a passivated cementaccelerator refers to particles of a cementitious material that haveundergone hydration while diluted in water such that they did notagglomerate and set into a hardened mass. Without being limited bytheory, it is believed that the passivated cement accelerator maygenerally be described as having a passivating layer of a hydrationreaction product (e.g., a passivating layer of calcium-silicate-hydratefor Portland cements) that encapsulates the particles of a cementitiousmaterial such that the cores of such particles are less available fordiffusion due to their encapsulation by the passivating layer, which maycreate a semi- or completely impermeable barrier until the passivatinglayer is at least partially removed by placing the passivated particlesinto alkali conditions. Further, the passivation process isolates theparticles of the cementitious material such that they do not form aninterlocking connected network that may set into a hardened mass, butreside instead as either discrete particles or as a localized looselyconnected network of a small number of particles (e.g., two, three, fourparticles, etc.) that possess only a limited connectivity that may bebroken if additional agitation is applied. In embodiments, thepassivated cement accelerator may generally be prepared by mixingcementitious materials with an abundance of water while stirring themixture at a sufficient rate and for a sufficient time such that thecementitious material and water are allowed to react, yet the particlesof the cementitious material are kept separate from one another, suchthat they do not form a hardened mass. The amount of water to add andthe amount of stirring or agitation required depends on the type ofcementitious material to be passivated. Generally, the minimum amount ofwater required is the amount necessary to keep the particles fromagglomerating; this amount may vary depending on the amount of agitationto be applied. Likewise, the minimum amount of agitation required is theamount necessary to keep the particles from settling; this amount mayvary depending on the amount of water that has been added.

Table 1 below shows an X-ray diffraction (“XRD) compositional analysisof a passivated cement accelerator that may be used in accordance withexample embodiments contrasted with an unhydrated Portland cement. Thepassivated cement accelerator shown in Table 1 is a passivated Portlandcement prepared in accordance with the procedure described below inExample 4 and aged to 127 days.

TABLE 1 XRD of a Passivated Cement Accelerator Unhydrated PassivatedPortland Cement Name Structure Cement Accelerator Hatrurite (C₃S) 54% 5%Larnite (C₂S) 26% 2% Brownmillerite (C₄AF) 17% 7% Gypsum CaSO₄2H₂O  3% —Portlandite Ca(OH)₂ — 15%  Ettringite Ca₆Al₂(SO₄)₃(OH₁₂) — 10%  24 H₂OAmorphous non-crystalline — 61%  Periclase MgO — — Anhydrite CaSO₄ — —

As illustrated in the table above, this example embodiment of apassivated cement accelerator may comprise C₃S in an amount of about 50%or less, C₂S in an amount of about 20% or less, and C₄AF in an amount ofabout 15% or less. In contrast, a typical unhydrated Portland cementwould be expected to comprise C₃S in an amount of about 54%, C₂S in anamount of about 26%, and C₄AF in about 17%. As can be seen in Table 1,the passivation process may convert the cementitious material from afully crystalline material to a material which is comprised partially ofcrystalline phases and partially of amorphous phases. Even after thepassivated cement had been in contact with water for 127 days there isstill evidence of un-hydrated crystalline material, which is present at˜14% of the composition. Without being limited by theory, the presenceof un-hydrated crystalline material may be explained by the passivationprocess. Ideally, during the passivation process, the amorphous phasesform a barrier of low diffusivity around the crystalline cement particle(e.g., in Portland cement, the amorphous barrier may be composed of thePortland cement reaction product calcium-silicate-hydrate “CSH”). Thisbarrier prevents the total hydration of the cement particle and providesa mechanism by which the passivated cement accelerator becomes activewhen introduced to cementitious slurries. Without being limited bytheory, it is believed that the mechanism through which the passivatedcement accelerator works is that when the accelerator is introduced toan alkaline cementitious slurry, the amorphous layer dissolves, orpartially dissolves, and the remaining crystalline cementitious materialis hydrated. The hydration of the crystalline cementitious material andthe inherent reactivity of the dissolved amorphous phases provide asignificant acceleration to the cementitious reactions taking place inthe alkaline cementitious slurry.

Any cementitious material discussed herein may be passivated. Forexample, the passivated cement accelerator may comprise Portlandcements, pozzolana cements, gypsum cements, high alumina contentcements, silica cements, slag cements, and any combination thereof. Asan example and without being limited by theory, it is believed that aPortland cement that has been passivated will comprise Portland cementparticles that are surrounded by a passivating layer ofcalcium-silicate-hydrate (CHS) gel. In this example, the passivatedPortland cement may not form a hardened mass until it is placed inalkaline conditions such that the alkalinity may remove at least aportion of the passivating layer.

Preparing the passivated cement accelerator comprises the addition of acementitious material to water. An abundance of water should be usedsuch that the particles of the cementitious material are not capable ofagglomerating, for example the water may be used in an amount of about60% by weight of the cementitious material to about 500% by weight ofthe cementitious material or more. The amount of water should besufficient to dilute the mixture enough so that the particles of thecementitious material generally should not agglomerate and bind to eachother, i.e. they remain discrete. For all practical purposes, the onlylimits to the amount of water that should be added are those limitsdetermined by logistical concerns. For example, the particles of thecementitious material should not be allowed to settle, therefore,although very large amounts of water may keep the particles fromagglomerating they may also require very vigorous agitation or largeamounts of suspension aids to keep the particles from settling. For allsystems therefore, the minimum amount of water is the amount necessaryto keep the particles from agglomerating, and the maximum amount ofwater is the largest amount where there is still a practical way to keepthe particles from settling. After the water has been added to thecementitious material the passivation process will commence. The mixturemay need to react for a period, for example, of about 4 hours to about12 hours. During the reaction phase, the mixture may need to be stirredeither continuously or intermittently. Any type of stirring or agitationmay be used provided it is sufficient to keep the cement particles fromsettling (e.g., magnetic stirrers and overhead stirrers may be used.)Additionally, a suspension agent, as discussed above, may be used to aidin suspending the cement particles. Use of the suspending agent may bein addition to or in substitution of agitation. Examples of suitablesuspending aids may include viscosifiers, such as those described abovewhich include swellable clays such as bentonite or biopolymers such ascellulose derivatives (e.g., hydroxyethyl cellulose, carboxymethylcellulose, carboxymethyl hydroxyethyl cellulose). An example of acommercially available viscosifier is SA-1015™ available fromHalliburton Energy Services, Inc., Houston, Tex.

The passivated cement accelerator should generally be passivated suchthat the hydraulic activity of the passivated particles has beenreduced. For example, the mixture of the passivated cement acceleratorand water may generally not set to form a hardened mass for an extendedperiod of time even without the presence of a set retarder. In someembodiments, the mixture of the passivated cement accelerator and watermay remain in a pumpable fluid state (i.e. consistency less than 70 Bcas discussed above) for an extended period of time. For example, themixture of the passivated cement accelerator and water may remain in apumpable fluid state in a range of about 1 day to about 10 days orlonger. Specifically, the mixture of the passivated cement acceleratorand water may remain in a pumpable state for about 1 day, about 3 days,about 7 days, about 10 days, or longer. In some embodiments, thismixture may be added to a cement composition as a liquid additive.Alternatively, the water may be removed from the passivated cementaccelerator in any sufficient manner (e.g., filtering, drying,suctioning, etc.) and the passivated cement accelerator may be kept as adry powder and stored for later use. The dry passivated cementaccelerator may be stored for weeks or months before use, for example,the dry passivated cement accelerator may be stored for about 4 monthsor longer.

In embodiments, the passivated cement accelerator may be added to thecement compositions in an amount in a range of about 0.1% to about 10%by weight of the cement in the cement composition. In specificembodiments, the passivated cement accelerator may be present in anamount ranging between any of and/or including any of about 0.1%, about0.5%, about 1%, about 2%, about 3%, about 5%, about 7%, or about 10% byweight of the cement in the cement composition. One of ordinary skill inthe art, with the benefit of this disclosure, will recognize theappropriate amount of passivated cement accelerator to include for achosen application.

In embodiments the passivated cement accelerator may be used to increaseearly strength development in a cement composition. It is to beunderstood that the passivated cement accelerator need not, but may,comprise the same or similar type of cement that is the object of thestrength enhancement provided by the passivated cement accelerator. Forexample, a passivated cement accelerator comprising passivated Portlandcement may be added to a cement composition comprising pumice, hydratedlime, and water. In particular embodiments, the cement composition maybe a set-delayed cement composition, as discussed in more detail above.As a further example, a passivated slag cement accelerator may be addedto a cement composition comprising high alumina content cement.

In some embodiments, the cement compositions may set to have a desirablecompressive strength after addition of the passivated cementaccelerator. Compressive strength is generally the capacity of amaterial or structure to withstand axially directed pushing forces. Thecompressive strength may be measured at a specified time afterpassivated cement accelerator has been added to the cement compositionand the resultant composition is maintained under specified temperatureand pressure conditions. Compressive strength can be measured by eitherdestructive or non-destructive methods. The destructive methodphysically tests the strength of cement composition samples at variouspoints in time by crushing the samples in a compression-testing machine.The compressive strength is calculated from the failure load divided bythe cross-sectional area resisting the load and is reported in units ofpound-force per square inch (psi). Non-destructive methods may employ aUCA™ ultrasonic cement analyzer, available from Fann Instrument Company,Houston, Tex. Compressive strength values may be determined inaccordance with API RP 10B-2, Recommended Practice for Testing WellCements, First Edition, July 2005.

By way of example, the cement compositions may develop a 24-hourcompressive strength in the range of from about 50 psi to about 5000psi, alternatively, from about 100 psi to about 4500 psi, oralternatively from about 500 psi to about 4000 psi. In some embodiments,the cement compositions may develop a compressive strength in 24 hoursof at least about 50 psi, at least about 100 psi, at least about 500psi, or more. In some embodiments, the compressive strength values maybe determined using destructive or non-destructive methods at atemperature ranging from about 40° F. (or lower) to about 500° F. (orhigher).

In some embodiments, the cement compositions may have desirablethickening times after addition of a passivated cement accelerator.Thickening time typically refers to the time a fluid, such as a cementcomposition, remains in a fluid state capable of being pumped. A numberof different laboratory techniques may be used to measure thickeningtime. A pressurized consistometer, operated in accordance with theprocedure set forth in the aforementioned API RP Practice 10B-2, may beused to measure whether a fluid is in a pumpable fluid state. Thethickening time may be the time for the treatment fluid to reach 70 Bcand may be reported as the time to reach 70 Bc. In some embodiments, thecement compositions may have a thickening time of greater than about 1hour, alternatively, greater than about 2 hours, alternatively greaterthan about 5 hours at 3,000 psi and temperatures in a range of fromabout 50° F. to about 400° F., alternatively, in a range of from about80° F. to about 250° F., and alternatively at a temperature of about140° F.

Optional embodiments of the passivated cement accelerator may be usedwith a cement set activator, such that an additive comprising apassivated cement accelerator and a cement set activator may be added tothe cement compositions. In embodiments where a cement set activator isused it may be necessary to stir the mixture of the passivated cementaccelerator and cement set activator while keeping the mixture cooled inan ice bath so as to mitigate any temperature increase. Alternatively, acement set activator may be added directly to the cement compositionbefore, after, or concurrently with a passivated cement accelerator. Theterm “cement set activator” or “activator,” as used herein, refers to anadditive that activates a set-delayed and/or retarded cement compositionand may also in certain systems accelerate the setting of set-delayed orretarded cement composition. By way of example, embodiments of aset-delayed and/or retarded cement composition may be activated to forma hardened mass in a time period in the range of from about 1 hour toabout 12 hours. For example, embodiments of a set-delayed and/orretarded cement composition may set to form a hardened mass in a timeperiod ranging between any of and/or including any of about 1 hour,about 2 hours, about 4 hours, about 6 hours, about 8 hours, about 10hours, or about 12 hours.

Examples of suitable cement set activators include, but are not limitedto: zeolites, amines such as triethanolamine, diethanolamine; silicatessuch as sodium silicate; zinc formate; calcium acetate; Groups IA andIIA hydroxides such as sodium hydroxide, magnesium hydroxide, andcalcium hydroxide; monovalent salts such as sodium chloride; divalentsalts such as calcium chloride; nanosilica (i.e., silica having aparticle size of less than or equal to about 100 nanometers);polyphosphates; and combinations thereof. In some embodiments, acombination of the polyphosphate and a monovalent salt may be used foractivation. The monovalent salt may be any salt that dissociates to forma monovalent cation, such as sodium and potassium salts. Specificexamples of suitable monovalent salts include potassium sulfate, andsodium sulfate. A variety of different polyphosphates may be used incombination with the monovalent salt for activation of the set-delayedcement compositions, including polymeric metaphosphate salts, phosphatesalts, and combinations thereof. Specific examples of polymericmetaphosphate salts that may be used include sodium hexametaphosphate,sodium trimetaphosphate, sodium tetrametaphosphate, sodiumpentametaphosphate, sodium heptametaphosphate, sodium octametaphosphate,and combinations thereof. A specific example of a suitable cement setactivator comprises a combination of sodium sulfate and sodiumhexametaphosphate. In particular embodiments, the activator may beprovided and added to the set-delayed cement composition as a liquidadditive, for example, a liquid additive comprising a monovalent salt, apolyphosphate, and optionally a dispersant.

Some embodiments may include a cement set activator comprising acombination of a monovalent salt and a polyphosphate. The monovalentsalt and the polyphosphate may be combined prior to addition to theset-delayed cement composition or may be separately added to theset-delayed cement composition. The monovalent salt may be any salt thatdissociates to form a monovalent cation, such as sodium and potassiumsalts. Specific examples of suitable monovalent salts include potassiumsulfate and sodium sulfate. A variety of different polyphosphates may beused in combination with the monovalent salt for activation of theset-delayed cement compositions, including polymeric metaphosphatesalts, phosphate salts, and combinations thereof, for example. Specificexamples of polymeric metaphosphate salts that may be used includesodium hexametaphosphate, sodium trimetaphosphate, sodiumtetrametaphosphate, sodium pentametaphosphate, sodiumheptametaphosphate, sodium octametaphosphate, and combinations thereof.A specific example of a suitable cement set activator comprises acombination of sodium sulfate and sodium hexametaphosphate.Interestingly, sodium hexametaphosphate is also known in the art to be astrong retarder of Portland cements. Because of the unique chemistry ofpolyphosphates, polyphosphates may be used as a cement set activator forembodiments of the set-delayed cement compositions disclosed herein. Theratio of the monovalent salt to the polyphosphate may range, forexample, from about 5:1 to about 1:25 or from about 1:1 to about 1:10.Embodiments of the cement set activator may comprise the monovalent saltand the polyphosphate salt in a ratio (monovalent salt to polyphosphate)ranging between any of and/or including any of about 5:1, 2:1, about1:1, about 1:2, about 1:5, about 1:10, about 1:20, or about 1:25.

In some embodiments, the combination of the monovalent salt and thepolyphosphate may be mixed with a dispersant and water to form a liquidadditive for activation of a set-delayed and/or retarded cementcomposition. Examples of suitable dispersants include, withoutlimitation, the previously described dispersants, such assulfonated-formaldehyde-based dispersants and polycarboxylated etherdispersants. One example of a dispersant is CFR-3™ dispersant availablefrom Halliburton Energy Services, Inc. Examples of suitablepolycarboxylated ether dispersants include Liquiment® 514L and 5581Fdispersants, available from BASF Corporation, Houston, Tex.

The liquid additive may function as a cement set activator. As discussedabove, a cement set activator may also accelerate the setting of theset-delayed and/or retarded cement. The use of a liquid additive toaccelerate a set-delayed and/or retarded cement is dependent upon thecompositional makeup of the liquid additive as well as the compositionalmakeup of the set-delayed and/or retarded cement. With the benefit ofthis disclosure, one of ordinary skill in the art should be able toformulate a liquid additive to activate and/or accelerate a set-delayedand/or retarded cement composition.

The cement set activator may be added to embodiments of a set-delayedcement composition in an amount sufficient to induce the set-delayedand/or retarded cement composition to set into a hardened mass. Incertain embodiments, the cement set activator may be added to theset-delayed and/or retarded cement composition in an amount in the rangeof about 0.1% to about 20% by weight of the cement. In specificembodiments, the cement set activator may be present in an amountranging between any of and/or including any of about 0.1%, about 1%,about 5%, about 10%, about 15%, or about 20% by weight of the cement.One of ordinary skill in the art, with the benefit of this disclosure,will recognize the appropriate amount of cement set activator to includefor a chosen application.

As will be appreciated by those of ordinary skill in the art,embodiments of the cement compositions may be used in a variety ofcementing operations such as surface cementing operations (e.g.,construction) and subterranean cementing operations (e.g., primary andremedial cementing). As an example, in some embodiments, a cementcomposition may be provided that comprises water, pumice, hydrated lime,a set retarder, and optionally a dispersant. A passivated cementaccelerator may be added to the cement composition. The cementcomposition comprising the passivated cement accelerator may then beallowed to set. In some embodiments, the cement composition may beintroduced into a subterranean formation and allowed to set therein. Asused herein, introducing the cement composition into a subterraneanformation includes introduction into any portion of the subterraneanformation, including, without limitation, into a wellbore drilled intothe subterranean formation, into a near wellbore region surrounding thewellbore, or into both.

In some embodiments, a cement composition may be provided that compriseswater, pumice, hydrated lime, a set retarder, and optionally adispersant. The cement composition may be stored, for example, in avessel or other suitable container. The cement composition may bepermitted to remain in storage for a desired time period. For example,the cement composition may remain in storage for a time period of about1 day or longer. For example, the cement composition may remain instorage for a time period of about 1 day, about 2 days, about 5 days,about 7 days, about 10 days, about 20 days, about 30 days, about 40days, about 50 days, about 60 days, or longer. In some embodiments, thecement composition may remain in storage for a time period in a range offrom about 1 day to about 7 days or longer. Thereafter, the cementcomposition may be activated, for example, by the addition of cement setactivator which may be a component of a passivated cement accelerator oradded in conjunction with a passivated cement accelerator. The cementcomposition may then be introduced into a subterranean formation, andallowed to set therein.

In primary cementing embodiments, for example, embodiments of the cementcomposition may be introduced into an annular space between a conduitlocated in a wellbore and the walls of a wellbore (and/or a largerconduit in the wellbore), wherein the wellbore penetrates thesubterranean formation. The cement composition may be allowed to set inthe annular space to form an annular sheath of hardened cement. Thecement composition may form a barrier that prevents the migration offluids in the wellbore. The cement composition may also, for example,support the conduit in the wellbore.

In remedial cementing embodiments, a cement composition may be used, forexample, in squeeze-cementing operations or in the placement of cementplugs. By way of example, the cement composition may be placed in awellbore to plug an opening (e.g., a void or crack) in the formation, ina gravel pack, in the conduit, in the cement sheath, and/or between thecement sheath and the conduit (e.g., a microannulus).

An embodiment may comprise a method of cementing comprising: providing acement composition comprising cement, water, and a passivated cementaccelerator; and allowing the cement composition to set.

An embodiment may comprise a cement composition comprising: a passivatedcement accelerator, water, and a cement.

An embodiment may comprise a passivated cementing system for cementingin a wellbore comprising: a passivated cement accelerator, a cementcomposition comprising cement and water, mixing equipment capable ofmixing the passivated cement accelerator and the cement composition, andpumping equipment for delivering the mixed passivated cement acceleratorand the cement composition to a wellbore.

Referring now to FIG. 1, preparation of a cement composition (which maybe set delayed or non-set delayed) in accordance with exampleembodiments will now be described. FIG. 1 illustrates a system 2 forpreparation of a cement composition and delivery to a wellbore inaccordance with certain embodiments. As shown, the cement compositionmay be mixed in mixing equipment 4, such as a jet mixer, re-circulatingmixer, or a batch mixer, for example, and then pumped via pumpingequipment 6 to the wellbore. In some embodiments, the mixing equipment 4and the pumping equipment 6 may be disposed on one or more cement trucksas will be apparent to those of ordinary skill in the art. In someembodiments, a jet mixer may be used, for example, to continuously mixthe lime/settable material with the water as it is being pumped to thewellbore. In set-delayed embodiments, a re-circulating mixer and/or abatch mixer may be used to mix the set-delayed cement composition, and apassivated cement accelerator may be added to the mixer as a liquid or apowder prior to pumping the cement composition downhole. The passivatedcement accelerator may comprise an activator. Alternatively theactivator may be added to the re-circulating mixer and/or a batch mixerbefore, after, or concurrently with the passivated cement accelerator.

An example technique for placing a cement composition into asubterranean formation will now be described with reference to FIGS. 2and 3. FIG. 2 illustrates surface equipment 10 that may be used inplacement of a cement composition in accordance with certainembodiments. It should be noted that while FIG. 2 generally depicts aland-based operation, those skilled in the art will readily recognizethat the principles described herein are equally applicable to subseaoperations that employ floating or sea-based platforms and rigs, withoutdeparting from the scope of the disclosure. As illustrated by FIG. 2,the surface equipment 10 may include a cementing unit 12, which mayinclude one or more cement trucks. The cementing unit 12 may includemixing equipment 4 and pumping equipment 6 (e.g., FIG. 1) as will beapparent to those of ordinary skill in the art. The cementing unit 12may pump a cement composition 14 through a feed pipe 16 and to acementing head 18 which conveys the cement composition 14 downhole.

Turning now to FIG. 2, the set-delayed or non-set-delayed cementcomposition 14 may be placed into a subterranean formation 20 inaccordance with example embodiments. As illustrated, a wellbore 22 maybe drilled into the subterranean formation 20. While wellbore 22 isshown extending generally vertically into the subterranean formation 20,the principles described herein are also applicable to wellbores thatextend at an angle through the subterranean formation 20, such ashorizontal and slanted wellbores. As illustrated, the wellbore 22comprises walls 24. In the illustrated embodiment, a surface casing 26has been inserted into the wellbore 22. The surface casing 26 may becemented to the walls 24 of the wellbore 22 by cement sheath 28. In theillustrated embodiment, one or more additional conduits (e.g.,intermediate casing, production casing, liners, etc.), shown here ascasing 30 may also be disposed in the wellbore 22. As illustrated, thereis a wellbore annulus 32 formed between the casing 30 and the walls 24of the wellbore 22 and/or the surface casing 26. One or morecentralizers 34 may be attached to the casing 30, for example, tocentralize the casing 30 in the wellbore 22 prior to and during thecementing operation.

With continued reference to FIG. 3, the cement composition 14 may bepumped down the interior of the casing 30. The cement composition 14 maybe allowed to flow down the interior of the casing 30 through the casingshoe 42 at the bottom of the casing 30 and up around the casing 30 intothe wellbore annulus 32. The cement composition 14 may be allowed to setin the wellbore annulus 32, for example, to form a cement sheath thatsupports and positions the casing 30 in the wellbore 22. While notillustrated, other techniques may also be utilized for introduction ofthe pozzolanic cement composition 14. By way of example, reversecirculation techniques may be used that include introducing the cementcomposition 14 into the subterranean formation 20 by way of the wellboreannulus 32 instead of through the casing 30.

As it is introduced, the cement composition 14 may displace other fluids36, such as drilling fluids and/or spacer fluids that may be present inthe interior of the casing 30 and/or the wellbore annulus 32. At least aportion of the displaced fluids 36 may exit the wellbore annulus 32 viaa flow line 38 and be deposited, for example, in one or more retentionpits 40 (e.g., a mud pit), as shown on FIG. 2. Referring again to FIG.3, a bottom plug 44 may be introduced into the wellbore 22 ahead of thecement composition 14, for example, to separate the cement composition14 from the fluids 36 that may be inside the casing 30 prior tocementing. After the bottom plug 44 reaches the landing collar 46, adiaphragm or other suitable device should rupture to allow thepozzolanic cement composition 14 through the bottom plug 44. In FIG. 3,the bottom plug 44 is shown on the landing collar 46. In the illustratedembodiment, a top plug 48 may be introduced into the wellbore 22 behindthe cement composition 14. The top plug 48 may separate the cementcomposition 14 from a displacement fluid 50 and also push the cementcomposition 14 through the bottom plug 44.

The exemplary cement compositions disclosed herein may directly orindirectly affect one or more components or pieces of equipmentassociated with the preparation, delivery, recapture, recycling, reuse,and/or disposal of the disclosed cement compositions. For example, thedisclosed cement compositions may directly or indirectly affect one ormore mixers, related mixing equipment, mud pits, storage facilities orunits, composition separators, heat exchangers, sensors, gauges, pumps,compressors, and the like used generate, store, monitor, regulate,and/or recondition the exemplary cement compositions. The disclosedcement compositions may also directly or indirectly affect any transportor delivery equipment used to convey the cement compositions to a wellsite or downhole such as, for example, any transport vessels, conduits,pipelines, trucks, tubulars, and/or pipes used to compositionally movethe cement compositions from one location to another, any pumps,compressors, or motors (e.g., topside or downhole) used to drive thecement compositions into motion, any valves or related joints used toregulate the pressure or flow rate of the cement compositions, and anysensors (i.e., pressure and temperature), gauges, and/or combinationsthereof, and the like. The disclosed cement compositions may alsodirectly or indirectly affect the various downhole equipment and toolsthat may come into contact with the cement compositions such as, but notlimited to, wellbore casing, wellbore liner, completion string, insertstrings, drill string, coiled tubing, slickline, wireline, drill pipe,drill collars, mud motors, downhole motors and/or pumps, cement pumps,surface-mounted motors and/or pumps, centralizers, turbolizers,scratchers, floats (e.g., shoes, collars, valves, etc.), logging toolsand related telemetry equipment, actuators (e.g., electromechanicaldevices, hydromechanical devices, etc.), sliding sleeves, productionsleeves, plugs, screens, filters, flow control devices (e.g., inflowcontrol devices, autonomous inflow control devices, outflow controldevices, etc.), couplings (e.g., electro-hydraulic wet connect, dryconnect, inductive coupler, etc.), control lines (e.g., electrical,fiber optic, hydraulic, etc.), surveillance lines, drill bits andreamers, sensors or distributed sensors, downhole heat exchangers,valves and corresponding actuation devices, tool seals, packers, cementplugs, bridge plugs, and other wellbore isolation devices, orcomponents, and the like.

To facilitate a better understanding of the present embodiments, thefollowing examples of certain aspects of some embodiments are given. Inno way should the following examples be read to limit, or define, theentire scope of the embodiments.

EXAMPLES Example 1

The following example describes a passivated cement accelerator andcement set activator composition comprising the following components:

TABLE 2 Passivated Cement Accelerator and Cement Set ActivatorCompositional Makeup Component Weight (g) Weight (%) Water 75.0 46.4Cementitious Material 30.0 18.6 Activator 56.5 35.0

The passivated cement accelerator was prepared by adding 30.0 grams ofClass H Portland cement to 75.0 grams of water. The mixture was allowedto react for 5 hours and was stirred such that the cement particles weresufficiently separated and unable to form a hardened mass. To thismixture, 56.5 grams of CaCl₂ were added and stirred into the mixturewhile cooling it in an ice bath to mitigate the exothermic releasecaused by the addition of the CaCl₂ to the water. In order todemonstrate that the mixture would maintain a pumpable fluid state andwould not set into a hardened mass, the mixture was placed in a sealedcontainer on a bench top and a visual inspection was made once per day.After 10 days the mixture was still in a pumpable fluid state.

The passivated cement accelerator comprising a cement set activator wasthen added to a set-delayed cement composition comprising the followingcomponents:

TABLE 3 Set-Delayed Cement Compositional Makeup Component Amount Unit*Water 60 % bwoC Pumice 100 % bwoC Lime 20 % bwoC Weighting Agent 2 %bwoC Retarder 1.25 % bwoC Co-Retarder 0.5 % bwoC Dispersant 0.6 % bwoCViscosifier 0.035 % bwoC *% bwoC = by weight of cement, for this systemthe cement is Pumice.

The composition had a density of 13.2 pounds per gallon. The weightingagent was Micromax® FF weight additive available from Halliburton EnergyServices, Inc., Houston, Tex. The cement retarder was Micro Matrix®Cement Retarder available from Halliburton Energy Services, Inc.,Houston, Tex. The cement co-retarder was HR®-5 Cement Retarder availablefrom Halliburton Energy Services, Inc., Houston, Tex. The dispersant wasLiquiment 5581F dispersant available from BASF, Florham Park, N.J. Theviscosifier was SA-1015™ suspending agent available from HalliburtonEnergy Services, Inc., Houston, Tex. After preparation of the cementcomposition, an experimental sample of the cement composition was mixedwith the passivated cement accelerator and the cement set activatorcomposition. Additionally, a control sample of the cement compositionwas mixed with only the cement set activator. After mixing, both cementcomposition samples were further conditioned in an atmosphericconditioner under the following parameters: 70 minutes at 183° F.followed by 60 minutes at 151° F. The samples were then poured into 1″by 2″ brass cylinders and cured for 24 hours at 160° F. and 3000 psi. inan autoclave. After the samples were cured, the destructive compressivestrength was measured by using a mechanical press to crush the samplesin accordance with the procedure set forth in API RP Practice 10B-2,Recommended Practice for Testing Well Cements. The results are presentedin Table 4 below.

TABLE 4 Compressive Strength Measurements Cement Set Passivated CementCompressive Activator Accelerator Density (ppg) Strength (psi) 5%*2.65%* 13.2 2082 5%* — 13.2 95 *% by weight of cement, for this systemthe cement is Pumice.

The results are an average of three experiments. The results show thatthe addition of a passivated cement accelerator increases the 24 hourcompressive strength more than the addition of the cement set activatoralone.

Example 2

The following example describes a passivated cement accelerator and acement set activator composition comprising the following components:

TABLE 5 Passivated Cement Accelerator and Cement Set ActivatorCompositional Makeup Component Weight (g) Weight (%) Water 75.0 46.4Cementitious Material 30.0 18.6 Activator 56.5 35.0

The passivated cement accelerator was prepared by adding 30.0 grams ofground granulated blast furnace slag to 75.0 grams of water. The mixturewas allowed to react for 5 hours and was stirred such that the cementparticles were sufficiently separated and unable to form a hardenedmass. To this mixture, 56.5 grams of CaCl₂ were added and stirred intothe mixture while cooling it in an ice bath to mitigate the exothermicrelease caused by the addition of the CaCl₂ to the water. In order todemonstrate that the mixture would maintain a pumpable fluid state andwould not set into a hardened mass, the mixture placed in a sealedcontainer on a bench top and a visual inspection was made once per day.After 2 days the mixture was still in a pumpable fluid state.

The passivated cement accelerator comprising a cement set activator wasthen added to a set-delayed cement composition comprising the followingcomponents:

TABLE 6 Set-Delayed Cement Compositional Makeup Component Amount Unit*Water 60 % bwoC Pumice 100 % bwoC Lime 20 % bwoC Weighting Agent 2 %bwoC Retarder 1.25 % bwoC Co-Retarder 0.5 % bwoC Dispersant 0.6 % bwoCViscosifier 0.035 % bwoC *% bwoC = by weight of cement, for this systemthe cement is the Pumice.

The composition had a density of 13.2 pounds per gallon (ppg). Theweighting agent was Micromax® FF weight additive available fromHalliburton Energy Services, Inc., Houston. Tex. The cement retarder wasMicro Matrix® Cement Retarder available from Halliburton EnergyServices, Inc., Houston, Tex. The cement co-retarder was HR®-5 CementRetarder available from Halliburton Energy Services, Inc., Houston, Tex.The dispersant was Liquiment 5581F dispersant available from BASF,Florham Park, N.J. The viscosifier was SA-1015™ suspending agentavailable from Halliburton Energy Services, Inc., Houston, Tex. Afterpreparation of the cement composition, an experimental sample of thecement composition was mixed with the passivated cement accelerator andthe cement set activator composition. Additionally, a control sample ofthe cement composition was mixed with only the cement set activator.After mixing, both cement composition samples were further conditionedin an atmospheric conditioner under the following parameters: 70 minutesat 183° F. followed by 60 minutes at 151° F. The samples were thenpoured into 1″ by 2″ brass cylinders and cured for 24 hours at 160° F.and 3000 psi. in an autoclave. After the samples were cured, thedestructive compressive strength was measured by using a mechanicalpress to crush the samples in accordance with the procedure set forth inAPI RP Practice 10B-2, Recommended Practice for Testing Well Cements.The results are presented in Table 7 below.

TABLE 7 Compressive Strength Measurements Cement Set Passivated CementCompressive Activator Accelerator Density (ppg) Strength (psi) 5%*2.65%* 13.2 1324 5%* — 13.2 95 *% by weight of cementitious materials,for this system the cement is Pumice.

The results are an average of three experiments. The results show thatpassivating slag for use as a cement accelerator increases the 24-hourcompressive strength more than the addition of the cement set activatoralone.

Example 3

The following example describes a passivated cement accelerator and acement set activator composition comprising the following components:

TABLE 8 Passivated Cement Accelerator and Cement Set ActivatorCompositional Makeup Component Weight (g) Weight (%) Water 75.0 46.4Cementitious Material 30.0 18.6 Activator 56.5 35.0 Viscosifier 0.030.02

The passivated cement accelerator was prepared by adding 30.0 grams ofClass H Portland cement to 75.0 grams of water and 0.03 grams of theviscosifier, SA-1015™ suspending agent available from Halliburton EnergyServices, Inc., Houston, Tex. The mixture was allowed to react for 5hours and was stirred such that the cement particles were sufficientlyseparated and unable to form a hardened mass. To this mixture, 56.5grams of CaCl₂ were added and stirred into the mixture while cooling itin an ice bath to mitigate the exothermic release caused by the additionof the CaCl₂ to the water.

The passivated cement accelerator comprising a cement set activator wasthen added to three different Class H Portland cement compositionscomprising the following components:

TABLE 9 Cement Compositional Makeup Component* Sample 1 Sample 2 Sample3 Water 38.1 37.9 37.7 Cement 100.0 100.0 100.0 Retarder 0.0 0.5 1.0 *%by weight of cement, for this system the cement is Class H Portlandcement.

Each sample had a density of 16.5 pounds per gallon. The cement retarderwas HR®-5 Cement Retarder available from Halliburton Energy Services,Inc., Houston, Tex. After preparation of each cement composition, eachcomposition was split into experimental and control samples. Theexperimental samples of the cement compositions were mixed with thepassivated cement accelerator and the cement set activator composition.The control samples of the cement compositions were mixed with only thecement set activator. After mixing, the cement composition samples werethen poured into 2″ by 4″ brass cylinders and cured for 24 hours at 80°F. in a water bath. After the samples were cured, the destructivecompressive strength was measured by using a mechanical press to crushthe samples in accordance with the procedure set forth in API RPPractice 10B-2, Recommended Practice for Testing Well Cements. Theresults are presented in Table 10 below.

TABLE 10 Compressive Strength Measurements Passivated Cement Set CementCompressive Composition Activator* Accelerator* Retarder* Strength (psi)Sample 1 3% — 0.0 2400 Sample 1 3% 1.6% 0.0 2714 Sample 2 3% — 0.5 DNS**Sample 2 3% 1.6% 0.5 3333 Sample 3 3% — 1.0 DNS** Sample 3 3% 1.6% 1.03229 *% by weight of cement, for this system the cement is Class HPortland cement; **DNS = Did not set.

The results are an average of three experiments. The results show thatthe addition of passivated cement accelerator increases the 24-hourcompressive strength more than the addition of the cement set activatoralone.

Example 4

The following example describes a passivated cement acceleratorcomposition comprising the following components:

TABLE 11 Passivated Cement Accelerator Compositional Makeup ComponentWeight (g) Weight (%) Water 750.0 70.7 Cementitious Material 300.0 28.3Viscosifier 10.6 1

The passivated cement accelerator was prepared by adding 300.0 grams ofClass H Portland cement to 750.0 grams of water and 10.6 grams of theviscosifier, SA-1015™ suspending agent available from Halliburton EnergyServices, Inc., Houston, Tex. The mixture was allowed to react for 5hours and was stirred such that the cement particles were sufficientlyseparated and unable to form a hardened mass. The passivated cementaccelerator was then added to a retarded calcium aluminate phosphatecement:

TABLE 12 Cement Compositional Makeup Component* Weight (g) % bwoC* Water311 39 Cement 800 100 Retarder 8 1 Co-Retarder 4 0.5 *% by weight ofcement, for this system the cement is the calcium aluminate phosphatecement.

The cement retarder was FE-2™ Cement Retarder available from HalliburtonEnergy Services, Inc., Houston, Tex. The co-retarder was an organicacid. After preparation of the composition, 1123 grams of the cementcomposition was added to 39.7 grams of the passivated cementaccelerator. The mixture was then stirred in Warring Blender at 4000 rpmfor 1 minute.

The rheological properties of the sample were measured using a Model 35AFann Viscometer and a No. 2 spring with a Fann Yield Stress Adapter(FYSA), in accordance with the procedure set forth in API RP Practice10B-2, Recommended Practice for Testing Well Cements. The results arepresented in Table 13 below.

TABLE 13 Rheological Measurements Time RPM 3 6 100 200 300 3D 6D 0 Hrs.↑ 3 4 9 15 20 — — 0 Hrs. ↓ 2 2 7 13 18 — — 0 Hrs. Avg. 2.5 3 8 14 19 1.51 2 Hrs. ↑ 2 3 15 25 35 — — 2 Hrs. ↓ 2 3 13 17 25 — — 2 Hrs. Avg. 2 3 1421 30 1   1

Introduction of a Portland cement to a calcium aluminate phosphatecement may result in gelation and/or flash setting. However, the resultsshow that the introduction of a passivated Portland cement did notresult in gelation or flash setting either immediately to or two hourspost mixing.

The composition was then split into experimental and control samples.The experimental sample of the cement composition was mixed with thepassivated cement accelerator. The control sample of the cementcomposition was not mixed with the passivated cement accelerator. Thecement composition samples were then poured into 1″ by 2″ brasscylinders and cured for 72 hours at room temperature. After the sampleswere cured, the destructive compressive strength was measured by using amechanical press to crush the samples in accordance with the procedureset forth in API RP Practice 10B-2, Recommended Practice for TestingWell Cements. The results are presented in Table 14 below.

TABLE 14 Compressive Strength Measurements Passivated Cement CompressiveComposition Accelerator* Strength (psi) Control 0.0% DNS** Experimental  1% 236.2 *% by weight of cement, for this system the cement is thecalcium aluminate phosphate cement; **DNS = Did not set.

The results are an average of three experiments. The results show thatthe addition of passivated cement accelerator increases the 72-hourcompressive strength even without the presence of a cement setactivator.

Example 5

The following example describes a passivated cement acceleratorcomposition comprising the following components:

TABLE 15 Passivated Cement Accelerator and Cement Set ActivatorCompositional Makeup Component Weight (g) Weight (%) Water 750.0 70.7Cementitious Material 300.0 28.3 Viscosifier 10.6 1

The passivated cement accelerator was prepared by adding 300.0 grams ofClass H Portland cement to 750.0 grams of water and 10.6 grams of theviscosifier, SA-1015™ suspending agent available from Halliburton EnergyServices, Inc., Houston, Tex. The mixture was allowed to react for 5hours and was stirred such that the cement particles were sufficientlyseparated and unable to form a hardened mass. The passivated cementaccelerator was then added to a non-retarded calcium aluminate phosphatecement:

TABLE 16 Cement Compositional Makeup Component* Weight (g) % bwoC* Water311 39 Cement 800 100 *% by weight of cement, for this system the cementis the calcium aluminate phosphate cement.

After preparation of the composition, 861 grams of the cementcomposition was added to 30.4 grams of the passivated cementaccelerator. The mixture was then stirred in Warring Blender at 4000 rpmfor 1 minute.

The rheological properties of the sample were measured using a Model 35AFann Viscometer and a No. 2 spring with a Fann Yield Stress Adapter(FYSA), in accordance with the procedure set forth in API RP Practice10B-2, Recommended Practice for Testing Well Cements. The results arepresented in Table 17 below.

TABLE 17 Rheological Measurements Time RPM 3 6 100 200 300 3D 6D 0 Hrs.↑ 16 21 30 38 45 — — 0 Hrs. ↓ 9 9 18 26 35 — — 0 Hrs. Avg. 12.5 15 24 3240 9 9 1 Hrs. ↑ 22 25 37 44 53 — — 1 Hrs. ↓ 9 9 23 34 48 — — 1 Hrs. Avg.15.5 17 30 39 50.5 9 9

The passivated cement accelerator did not result in either gelation or aflash set. The mixture was more viscous than the retarded cementcomposition of Example 4, yet the composition was still fluid and therheology measurements were largely unchanged even after one hour.

The composition was then split into experimental and control samples.The experimental sample of the cement composition was mixed with thepassivated cement accelerator. The control sample of the cementcomposition was not mixed with the passivated cement accelerator. Thecement composition samples were then poured into 1″ by 2″ brasscylinders and cured for 24 hours in a water bath at 140° F. After thesamples were cured, the destructive compressive strength was measured byusing a mechanical press to crush the samples in accordance with theprocedure set forth in API RP Practice 101-2, Recommended Practice forTesting Well Cements. The results are presented in Table 18 below.

TABLE 18 Compressive Strength Measurements Passivated Cement CompressiveComposition Accelerator* Strength (psi) Control 0.0% DNS** Experimental  1% 244.66 *% by weight of cement, for this system the cement is thecalcium aluminate phosphate cement; **DNS = Did not set.

The results are an average of three experiments. The results show thatthe addition of passivated cement accelerator increases the 24-hourcompressive strength even without the presence of a cement setactivator.

Example 6

To show that the particles of a cementitious material in a passivatedcement accelerator cannot have been passivated, the following experimentwas performed. A passivated cement accelerator composition was preparedthat comprises the following components:

TABLE 19 Passivated Cement Accelerator Compositional Makeup ComponentWeight (g) Weight (%) Water 750.0 70.7 Cementitious Material 300.0 28.3Viscosifier 10.6 1

The passivated cement accelerator was prepared by adding 300.0 grams ofClass H Portland cement to 750.0 grams of water and 10.6 grams of theviscosifier, SA-1015™ suspending agent available from Halliburton EnergyServices, Inc., Houston, Tex. The mixture was allowed to react for 5hours and was stirred such that the cement particles were sufficientlyseparated and unable to form a hardened mass.

After preparation, the sample was aged for 5 hours and then visuallyinspected. The sample was observed to be both flowable and pumpable. Therheological properties of the sample were then measured using a Model35A Fann Viscometer and a No. 2 spring with a Fann Yield Stress Adapter(FYSA), in accordance with the procedure set forth in API RP Practice10B-2, Recommended Practice for Testing Well Cements. The results arepresented in Table 20 below.

TABLE 20 5 Hour Rheology Measurements for a Passivated CementAccelerator RPM 3 6 100 200 300 600 VAV_(100 rpm) (cp)* PCA aged 11 1220 24 29 41 507 5 hours 9 10 19 24 31 *VAV_(100 rpm) = volume averageviscosity at 100 rpm in centipoise.

The slurry was then aged for 127 days with intermittent (<3 times aweek) agitation (i.e. stirring). After which the slurry was visuallyinspected and observed to still be both flowable and pumpable. Rheologymeasurements were taken again using the same protocol and parameters asdescribed above. The results are presented in Table 21 below.

TABLE 21 127 Day Rheology Measurements for a Passivated CementAccelerator RPM 3 6 100 200 300 600 VAV_(100 rpm) (cp)* PCA aged 7 11 3371 84 98 793 127 days 4 6 28 63 84 *VAV_(100 rpm) = volume averageviscosity at 100 rpm in centipoise.

Although there was a slight increase in viscosity after 127 days, thesample did not set into a hardened mass and has been observed to besuccessfully passivated.

It should be understood that the compositions and methods are describedin terms of “comprising,” “containing,” or “including” variouscomponents or steps, the compositions and methods can also “consistessentially of” or “consist of” the various components and steps.Moreover, the indefinite articles “a” or “an,” as used in the claims,are defined herein to mean one or more than one of the element that itintroduces.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, whenever a numerical range with alower limit and an upper limit is disclosed, any number and any includedrange falling within the range are specifically disclosed. Inparticular, every range of values (of the form, “from about a to aboutb,” or, equivalently, “from approximately a to b,” or, equivalently,“from approximately a-b”) disclosed herein is to be understood to setforth every number and range encompassed within the broader range ofvalues even if not explicitly recited. Thus, every point or individualvalue may serve as its own lower or upper limit combined with any otherpoint or individual value or any other lower or upper limit, to recite arange not explicitly recited.

Therefore, the present embodiments are well adapted to attain the endsand advantages mentioned as well as those that are inherent therein. Theparticular embodiments disclosed above are illustrative only, as thepresent embodiments may be modified and practiced in different butequivalent manners apparent to those skilled in the art having thebenefit of the teachings herein. Although individual embodiments arediscussed, all combinations of each embodiment are contemplated andcovered by the disclosure. Furthermore, no limitations are intended tothe details of construction or design herein shown, other than asdescribed in the claims below. Also, the terms in the claims have theirplain, ordinary meaning unless otherwise explicitly and clearly definedby the patentee. It is therefore evident that the particularillustrative embodiments disclosed above may be altered or modified andall such variations are considered within the scope and spirit of thepresent disclosure. If there is any conflict in the usages of a word orterm in this specification and one or more patent(s) or other documentsthat may be incorporated herein by reference, the definitions that areconsistent with this specification should be adopted.

What is claimed is:
 1. A method of cementing comprising: providing acement composition comprising cement, water, and a passivated cementaccelerator; and allowing the cement composition to set.
 2. The methodaccording to claim 1 wherein the cement composition further comprises atleast one set retarder selected from the group consisting of aphosphonic acid, a phosphonic acid derivative, a lignosulfonate, a salt,an organic acid, a carboxymethylated hydroxyethylated cellulose, asynthetic co- or ter-polymer comprising sulfonate and carboxylic acidgroups, a borate compound, and any mixture thereof.
 3. The methodaccording to claim 1 wherein the cement composition further comprises atleast one cement set activator selected from the group consisting ofcalcium chloride, triethanolamine, sodium silicate, zinc formate,calcium acetate, sodium hydroxide, sodium sulfate, nanosilica, sodiumhexametaphosphate, and any combinations thereof
 4. The method accordingto claim 1 wherein the cement composition further comprises at least onedispersant selected from the group consisting of asulfonated-formaldehyde-based dispersant, a polycarboxylated etherdispersant, and any combination thereof.
 5. The method according toclaim 1, wherein the passivated cement accelerator is selected from thegroup consisting of passivated Portland cement, passivated pozzolanacement, passivated gypsum cement, passivated high alumina contentcement, passivated silica cement, passivated slag cement, anycombination thereof.
 6. The method according to claim 1 wherein thecement is selected from the group consisting of a Portland cement, apozzolana cement, a gypsum cement, a high alumina content cement, asilica cement, a slag cement, and any combination thereof.
 7. The methodaccording to claim 1 wherein the passivated cement accelerator isprovided in a liquid additive further comprising a viscosifier.
 8. Themethod according to claim 1 wherein the passivated cement acceleratorcomprises passivated Portland cement, wherein the cement comprisepumice, and wherein the cement composition further comprises hydratedlime, a lignosulfonate, and calcium chloride.
 9. The method according toclaim 1 further comprising preparing the cement composition by mixing apassivated cement accelerator with at least the cement and the water.10. The method according to claim 1 further comprising preparing thepassivated cement accelerator by a process comprising mixing acementitious material with water and agitating the mixture of thecementitious material and water such that a passivating layer is formedon at least a portion of the cementitious material.
 11. The methodaccording to claim 1 further comprising introducing the cementcomposition into a subterranean formation, wherein the cementcomposition sets in the subterranean formation.
 12. The method accordingto claim 1 wherein the cement composition is used in a primary cementingoperation.
 13. A cement composition comprising: a passivated cementaccelerator, water, and a cement.
 14. The composition according to claim13 further comprising at least one set retarder selected from the groupconsisting of a phosphonic acid, a phosphonic acid derivative, alignosulfonate, a salt, an organic acid, a carboxymethylatedhydroxyethylated cellulose, a synthetic co- or ter-polymer comprisingsulfonate and carboxylic acid groups, a borate compound, and any mixturethereof.
 15. The composition according to claim 13 further comprising atleast one cement set activator selected from the group consisting ofcalcium chloride, triethanolamine, sodium silicate, zinc formate,calcium acetate, sodium hydroxide, sodium sulfate, nanosilica, sodiumhexametaphosphate, and any combinations thereof
 16. The compositionaccording to claim 13 further comprising at least one dispersantselected from the group consisting of a sulfonated-formaldehyde-baseddispersant, a polycarboxylated ether dispersant, and any combinationthereof.
 17. The composition according to claim 13 wherein thepassivated cement accelerator is selected from the group consisting ofpassivated Portland cement, passivated pozzolana cement, passivatedgypsum cement, passivated high alumina content cement, passivated silicacement, passivated slag cement, any combination thereof.
 18. Thecomposition according to claim 13 wherein the cement is selected fromthe group consisting of a Portland cement, a pozzolana cement, a gypsumcement, a high alumina content cement, a silica cement, a slag cement,and any combination thereof.
 19. The composition according to claim 13wherein the passivated cement accelerator comprises passivated Portlandcement, wherein the cement comprise pumice, and wherein the cementcomposition further comprises hydrated lime, a lignosulfonate, andcalcium chloride.
 20. A passivated cementing system for cementing in awellbore comprising: a passivated cement accelerator, a cementcomposition comprising cement and water, mixing equipment capable ofmixing the passivated cement accelerator and the cement composition and,pumping equipment for delivering the mixed passivated cement acceleratorand the cement composition to a wellbore.
 21. The system according toclaim 20 wherein the cement composition further comprises at least oneset retarder selected from the group consisting of a phosphonic acid, aphosphonic acid derivative, a lignosulfonate, a salt, an organic acid, acarboxymethylated hydroxyethylated cellulose, a synthetic co- orter-polymer comprising sulfonate and carboxylic acid groups, a boratecompound, and any mixture thereof.
 22. The system according to claim 20wherein the passivated cement accelerator is present in a liquidadditive further comprising at least one cement set activator selectedfrom the group consisting of calcium chloride, triethanolamine, sodiumsilicate, zinc formate, calcium acetate, sodium hydroxide, sodiumsulfate, nanosilica, sodium hexametaphosphate, and any combinationsthereof.
 23. (canceled)